Polymerization of 3-methoxthiophene (mot) monomer on poly-(acrylonitrile -co-itaconic acid) matrix and method for nano fiber derivative by method of electro-spinning of produced nano-particulates

ABSTRACT

The nano-fibre derivative method includes polymerization of 3-methoxthiophene (MOT) monomer on Poly(acrylonitrile co-itaconic acid) matrix and by use of electro-spinning of the produced nano-particulate.

CROSS-REFERENCE TO RELATED APPLICATIONS

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BACKGROUND OF THE INVENTION 1. Field of the Invention

The invention relates to nano-fiber derivative method by means of polymerization of 3-methoxthiophene (MOT) monomer on Poly(acrylonitrile co-itaconic acid) matrix and by use of electro-spinning of the produced nano-particulate.

2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 37 CFR 1.98

Since conductive polymers have broad area of use in super capacitor and electro chromatic instruments, conductive polymers have been studied comprehensively since 1970s.

In literature studies were conducted on electro-chemical polymerization of 3-methoxthiophene monomer of conductive monomers. The electro-chemical polymerization was made only in organic solvents such as acetonitrile and propylene carbonate for many years because 3-methoxthiophene monomer has low solubility in water.

Non-polymerization of 3-methoxthiophene monomer in wet micelle medium is a big disadvantage. By time water solubility of thiophene derivatives in water was increased by adding anti-ionic surface active agents (Sodium dodecyl sulfate), and potentials to start oxidization were reduced. Thus electro polymerization of 3-methoxthiophene monomer in water medium could be realized.

Due to low water solubility of said monomer 3-methoxthiophene and having oxidization potential higher than water, electro polymerization could not be realized.

Organic solvent medium such as acetonitrile and propylene carbonate was used for synthesizing poly(3-methoxthiophene) polymer for many years. Not being capable to work with 3-methoxthiophene monomer in water medium without any chemical was a disadvantage in economics and ecological terms.

There is no study concerning nano-fiber production by use of electro-spinning method due to difficulty in polymerization of 3-methoxthiophene monomer and processing on its own. This led to restriction in area of use of nano-fibers which will have conductivity feature.

In literature Korean Patent application numbered KR101447078 discloses a study on production of Poly-acrylonitrile (PAN) based carbon fiber which is of a high electro conductivity and considerably robust structure In said patent application a monomer mixture consisting of acrylonitrile, methyl acrylate ve itaconic acid monomer is used and polymerization is initiated by adding azobisisobutyronitrile starter. It is understood that the polymerization method used under this study is not emulsion polymerization and particularly use of ‘azobisisobutyronitrile’ is clearly seen.

Also in literature, Korean Patent application numbered KR20040040692 aims to provide ultramicro nano fiber production by use of both thermoplastic resin and thermoset resin. Electro-blown method is used in nano-fiber production. In this method the solvent prepared by solving polymer in a solution in advance is fed to spinning cap. Then high voltage and compressed air is applied underneath of spinning cap and collection of nano fibers at collector is provided by means of blowing.

Also in Literature Korean Patent application numbered KR20110074282 provides production of polyvinyl alcohol nano fibers by means of electrospinning method, then adds metallic ion effect into the nano fibers by means of submersion method and thereafter forms polypyrole/Poly(3,4 ethylene dioxide thieophene) nano tube members in polyvinyl nano fibers by means of vapor deposition polymerization method. This embodiment has magnetic characteristic and is aimed to be used in heavy metal filtering process.

Also in literature Korean patent application numbered KR20120094807 discloses a method for production of nano-fibers consisting of polymer characterized in that it contains phase changing material and super absorption in order to enhance strength against load pressure. In this respect, firstly nanocapsule consisting of phase changing material is formed. Then nanofiber production is made from nanucapsules provided from electrospinning method. Polymers of super absorbing feature is covered onto produced nanofibers by means of spray covering method. Lastly, the thermal and ultraviolet studies of the covered nanofiber were conducted.

Also in literature under the US patent application numbered US2013149532A1, two different monomer solutions are supplied to different injectors and then polymeric fiber comes from one single nozzle. In this method, no polymerization process is applied to monomers before process of preparing solution. After solutions are supplied in monomer form, fiber formation is provided in a manner conforming to polymeric fiber form inter-polymerized according to interfacial polymerization and obtained from a single polymer.

However, said literature does not include production of nanofibers after synthesizing Poly-(acrylonitrile-co-itaconic acid)/Poly(3-methoxthiophene) Nan composite structure and 3-methoxthiophene conductive monomer on Poly(Acrylonitrile-co-itaconic Acid) polymer in water medium.

For the above mentioned reasons, a nanofiber production method has been needed.

BRIEF SUMMARY OF THE INVENTION

From this status of the related art, the purpose of the invention is to disclose nanofiber derivative eliminating the current disadvantages.

Another purpose of the invention is to disclose a structure facilitating 3-methoxthiophene monomer capability to be processed and developing use of it.

A further purpose of the invention is to disclose a structure giving contribution to stabilization of loaded particles such as anion and cation radicals by help of ability to use micelle medium.

Another purpose of the invention is to disclose a structure allowing production of nanofiber from nano composite of Poly(Acrylonitrile-co-itaconic Acid/Poly(3-methoxthiophene) by use of electrospinning method.

A further purpose of the invention is to disclose a structure providing advantage for several applications requiring electro-active feature by help of capacitive feature of the obtained nanofiber.

Another purpose of the invention is to disclose a structure providing elimination of electrification by means of fractioning by means of covering the produced nanofibers on the plastic material surface.

A further purpose of the invention is to disclose a structure providing electrostatic or electromagnetic protection.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is an illustrative schematic view of emulsion polymerization of the invention.

FIG. 2 is an illustrative schematic view of synthesis of 3-methoxthiophene on P(AN-co-IA) matrix polymer by means of in-situ polymerization method.

FIG. 3 is an illustrative schematic view of electrospinning.

FIG. 4 is a schematic view of the formula, according to the present invention.

FIG. 5 is a schematic illustration of the formula, according to the present invention.

REFERENCE NUMBERS

-   A Emulsion Polymerization Mechanism -   1 Itaconic Acid Applicator -   2 Acrylonitrile Applicator -   3 APS Applicator -   4 Sodium Dodecylbenzene Sulfonate (SDBS) Applicator -   5 Polymer Solvent Applicator -   6 Needle -   7 Collector

DETAILED DESCRIPTION OF THE INVENTION

It should be noted in the following description that like or the same reference numerals in different embodiments denote the same or similar features. In this detailed description, novelty being subject of this invention has been disclosed solely for the purpose of better understanding of the subject and with samples described in a manner not causing any restrictive effect.

The invention is a nano-fiber derivative method by means of polymerization of 3-methoxthiophene (MOT) monomer on Poly(acrylonitrile co-itaconic acid) matrix and by use of electro-spinning of the produced nano-particulate and it is characterized in that it consists of method steps of:

-   -   Obtaining Poly (Acrylonitrile-co-Itaconic Acid) P(AN-co-IA)         co-polymer (matrix) by polymerization of acrylonitrile and         itaconic acid monomers emulsion in water medium by use of         polymerization,     -   Obtaining Poly (Acrylonitrile-co-Itaconic Acid)/Poly         (3-methoxthiophene) nano-composite structure by covering         3-methoxthiophene monomer on P(AN-co-IA) copolymer (matrix) by         in-situ polymerization method     -   Settling, drying the nano composite solution and transforming         into powder form,     -   Dissolution of Poly (Acrylonitrile-co-Itaconic         Acid)/Poly(3-methoxthiophene) polymer settled and dried to         prepare solution in N, N Dimethylformamide (DMF) in a manner of         5% by mass     -   Realizing formation of nanofiber by electrospinning method.

FIG. 1 shows an illustrative view of emulsion polymerization of the invention.

FIG. 2 indicates an illustrative view of synthesis of 3-methoxthiophene on P(AN-co-IA) matrix polymer by means of in-situ polymerization method.

FIG. 3 shows an illustrative view of electrospinning

In the application disclosed under the invention, in the first step Poly (Acrylonitrile-co-Itaconic Acid) P(AN-co-IA) co-polymer (matrix) is obtained by polymerization of acrylonitrile and itaconic acid monomers emulsion in water medium by use of polymerization.

Formula concerning said components is shown in FIG. 4 and FIG. 5.

Then Poly (Acrylonitrile-co-Itaconic Acid)/Poly (3-methoxthiophene) nano-composite structure is obtained by covering 3-methoxthiophene monomer on P(AN-co-IA) copolymer (matrix) by in-situ polymerization method.

Then the nano composite solution is settled, dried and transforming into powder form. In stage of nanofiber production, Poly (Acrylonitrile-co-Itaconic Acid)/Poly(3-methoxthiophene) polymer settled and dried to prepare solution in N, N Dimethylformamide (DMF) is dissolved in a manner to have 5% by mass, and then nanofiber production is provided by applying electrospinning method.

In the detailed application of the invention, first of all Poly(Acrylonitrile-co-Itaconic Acid) copolymer is synthesized by use of emulsion polymerization mechanism (A). Total 0.1% mol monomer-Acrylonitrile (AN) and Itaconic Acid (IA) is used. Said AN and IA is placed in said emulsion polymerization mechanism (A) container by use of Itaconic Acid Applicator (1) and Acrylonitrile Applicator (2).

As surfactant active agent 1.0766 g Sodium Dodecylbenzene Sulfonate (SDBS) and 0.1301 g IA and 6.5 ml AN is used in 150 ml water medium. Surfactant active agent SDBS is located inside SDBS applicator (4).

Said components are added respectively and mixed at magnetic mixer for 30 minutes upon each adding. Then the temperature of the solution is risen to 70° C.

When solution temperature 70° C., 3.423 g AmonyumPerSulfate (APS) is added as starter by means of APS Applicator (3). Polymerization process is continued at 70° C. for 3 hours. After 3 hours, the obtained polymer latex is divided into 10 equal beaker.

77.6 μl, 116.4 μl and 155.2 μl 3-methoxthiophene are separately added to 3 beakers equally and respectively and mixed at magnetic mixer at room temperature for 72 hours.

Upon 72 hours, the produced nano-particulars are settled by help of ethanol and ethanol and water is flushed one by the other and dried at 60° C. at vacuum drying oven.

Polymerization efficiencies are calculated as 70%, 74% and 76% respectively for 77.6 μl, 116.4 μl and 155.2 μl 3-methoxthiophene.

Nano-particulates of settled and dried Poly (Acrylonitrile-co-Itaconic Acid)/Poly(3-methoxthiophene)(P(AN-co-IA)/PMOT) are dissolved in N, N Dimetylformamide (DMF) solution so as to have it 5% by mass. Furthermore, solution of Polyacrylonitrile (PAN) is prepared in DMF medium to have 5% by mass.

P(AN-co-IA)/PMOT and PAN solutions are mixed and mixed by magnetic mixer at room temperature for 2 hours.

The obtained polymer solution is subjected to electrospinning operation by use of 15 kV voltage, 1.0 ml/h supply rate through polymer solution applicator (5). The distance between needle (6) and collector (7) is determined as 10 cm.

High electric current is applied to polymer solution supplied from a polymer solution applicator (5) to needle (6) in electrospinning method. The solution is collected at a collector (7) at a certain distance and in high electrical (DC) field by help of a pump.

PAN-P(AN-co-IA)/PMOT nanofibers are obtained after electrospinning operation. 

1. A method to obtain a nano-fibre derivative comprises the steps of: polymerizing 3-methoxthiophene (MOT) monomer on Poly(acrylonitrile co-itaconic acid) matrix; and electro-spinning of produced nano-particulate, wherein the step of polymerizing comprises the steps of: obtaining Poly (Acrylonitrile-co-Itaconic Acid) P(AN-co-IA) co-polymer (matrix) by polymerization of acrylonitrile and itaconic acid monomers emulsion in water medium by use of polymerization, obtaining Poly (Acrylonitrile-co-Itaconic Acid)/Poly (3-methoxthiophene) nano-composite structure by covering 3-methoxthiophene monomer on P(AN-co-IA) copolymer (matrix) by in-situ polymerization method, settling, drying the nano composite solution and transforming into powder form, dissolution of Poly (Acrylonitrile-co-Itaconic Acid)/Poly(3-methoxthiophene) polymer settled and dried to prepare solution in N, N Dimethylformamide (DMF) in a manner of 5% by mass and Realizing formation of nanofiber by electrospinning method.
 2. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of synthesizing all Poly(Acrylonitrile-co-Itaconic Acid) copolymer by use of emulsion polymerization mechanism (A).
 3. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of adding 1.0766 g Sodium Dodecylbenzene Sulfonate (SDBS) as surfactant agent 0.1301 g IA and 6.5 ml Acrylonitrile in 150 ml water medium.
 4. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of mixing at magnetic mixer for 30 minutes upon each agent adding.
 5. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of rising temperature of the solution to 70° C.
 6. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of adding 3.423 g AmoniumPerSulphate (APS) as initiator.
 7. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of continuing Polymerization process at 70° C. for 3 hours.
 8. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of dividing the obtained polymer latex into 10 equal beaker.
 9. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of separately adding 77.6 μl, 116.4 μl and 155.2 μl 3-methoxthiophene to 3 beakers equally and respectively and mixing at magnetic mixer at room temperature for 72 hours.
 10. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of settling the produced nano-particulars by help of ethanol and flushing by ethanol and water one by the other and drying at 60° C. at vacuum drying oven.
 11. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of mixing P(AN-co-IA)/PMOT and PAN solutions and mixing by magnetic mixer at room temperature for 2 hours.
 12. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of subjecting the obtained polymer solution to electrospinning operation by application of 15 kV voltage, 1.0 ml/h supply rate through polymer solution applicator (5).
 13. The method to obtain the nanofiber derivative according to claim 1, further comprising the step of obtaining PAN-P(AN-co-IA)/PMOT nanofibers after electrospinning operation. 